全文获取类型
收费全文 | 103105篇 |
免费 | 8415篇 |
国内免费 | 6698篇 |
专业分类
化学 | 27382篇 |
晶体学 | 330篇 |
力学 | 7318篇 |
综合类 | 1565篇 |
数学 | 58808篇 |
物理学 | 22815篇 |
出版年
2024年 | 173篇 |
2023年 | 935篇 |
2022年 | 2456篇 |
2021年 | 2427篇 |
2020年 | 2397篇 |
2019年 | 2608篇 |
2018年 | 2255篇 |
2017年 | 2438篇 |
2016年 | 2721篇 |
2015年 | 2410篇 |
2014年 | 4120篇 |
2013年 | 7657篇 |
2012年 | 4374篇 |
2011年 | 5202篇 |
2010年 | 4877篇 |
2009年 | 6035篇 |
2008年 | 6418篇 |
2007年 | 6532篇 |
2006年 | 5400篇 |
2005年 | 4511篇 |
2004年 | 3952篇 |
2003年 | 3992篇 |
2002年 | 6211篇 |
2001年 | 3313篇 |
2000年 | 2807篇 |
1999年 | 2519篇 |
1998年 | 2366篇 |
1997年 | 2007篇 |
1996年 | 1681篇 |
1995年 | 1311篇 |
1994年 | 1195篇 |
1993年 | 1048篇 |
1992年 | 1004篇 |
1991年 | 792篇 |
1990年 | 663篇 |
1989年 | 513篇 |
1988年 | 516篇 |
1987年 | 414篇 |
1986年 | 419篇 |
1985年 | 595篇 |
1984年 | 488篇 |
1983年 | 304篇 |
1982年 | 493篇 |
1981年 | 649篇 |
1980年 | 569篇 |
1979年 | 619篇 |
1978年 | 489篇 |
1977年 | 366篇 |
1976年 | 316篇 |
1973年 | 219篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
971.
Conformations of 2-methoxytetrahydropyran as a model for the six-membered ring in aldopyranosides have been calculated by the PCILO method using the algorithm of the conjugated gradient to optimize the geometry. The calculated geometry of the fourteen basic forms of 2-methoxytetrahydropyran was found to be in agreement with the available data obtained by X-ray diffraction of pyranosides. The results indicate differences in the geometry of 2-methoxytetrahydropyran resulting from the change of the axial vs. equatorial position of the methoxyl group. These changes are particularly meaningful in the values of bond angles and they are in agreement with the anomeric and exoanomeric effects. The experimentally found differences in the energies of an axial (4
C
1) and equatorial (1
C
4) conformer, G = 2.9–3.7 kJ/mol, and the dipole moment, = 1.20 ± 0.05 D (1D = 3.33 10–30mAs) agree well with the calculated values E = 3.18 kJ/mol and <> = 1.18 D which, in turn, suggest that the axial conformer is preferred over the equatorial one by a ratio a:e = 78:22. 相似文献
972.
G. G. Danagulyan D. A. Tadevosyan F. S. Kinoyan 《Chemistry of Heterocyclic Compounds》2006,42(6):782-787
Intermediate recyclization products were obtained in a study of the Kost-Sagitullin rearrangement of a series of 1,2-dialkylpyrimidinium
iodides. The initial attack of the nucleophile leads to the formation of products of the addition of the hydroxyl group, namely,
the corresponding pseudo bases. Heating one of these intermediates in ethanol or in the presence of primary amines leads to
rearrangement to give a pyridone derivative. Upon heating in chloroform, the pseudo bases readily lose a water molecule and
are converted to anhydro bases, namely, derivatives of 1-alkyl-1,2-dihydro-2-methylidenepyrimidine.
__________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 894–900, May, 2006. 相似文献
973.
Eckhard Herrmann Moein Nouaman Zdirad
k Gisbert Großmann Gisela Ohms 《无机化学与普通化学杂志》1994,620(11):1879-1888
Tetraarylesters of μ-Imido-Diphosphoric Acid and its Thio Derivatives — Structure Investigations New O,O′,O″,O?-tetratolyl- and ditolyl-diphenylesters of the μ-imido-diphosphoric acid and its mono and dithio derivatives were synthesized, compared with the corresponding tetraphenylesters and investigated by 1H, 13C, and 31P NMR spectroscopy and X-ray crystal structure analysis. Structures of the O,O′,O″,O?-tetrakis-(2-methyl-phenyl)-μ-imidodiphosphate, 1b , as well as of the corresponding ortho-, meta- and para-tolylesters of the μ-imido-monothiodiphosphoric acid ( 2a , 2b , 2c ) were determined. All the compounds form dimers via N? H…?O hydrogen bonds in the crystal as well as in nonpolar solvents. The distances around the phosphorus atoms rise with decreasing electronegativity of the phosphorus substituents. Signs of the 2JP? N? P coupling constants were determined by 13C{1H, 31P} triple resonance experiments for some compounds. These constants become more negative owing to substitution of a phosphoryl by a thiophosphoryl group. 相似文献
974.
The parallel between orbital first and second electric moments and statistical first and second central moments is noted. Three measures of orbital spatial distribution in terms of their moments are proposed, and applied to the LMO's in a series of ten-electron hydrides. Consistent differences between bond and lone pair distributions are found. Using the statistical interpretation, for each LMO an effective solid angle around the central atom is postulated. 相似文献
975.
Ioannis?Z.?EmirisEmail author Theodoros?G.?Nikitopoulos 《Journal of mathematical chemistry》2005,37(3):233-253
Three-dimensional molecular structure is fundamental in chemical function identification and computer-aided drug design. The enumeration of a small number of feasible conformations provides a rigorous way to determine the optimal or a few acceptable conformations. Our contribution concerns a heuristic enhancement of a method based on distance geometry, typically in relation with experiments of the NMR type. Distance geometry has been approached by different viewpoints; ours is expected to help in several subtasks arising in the process that determines 3D structure from distance information. More precisely, the input to our algorithm consists of a set of approximate distances of varying precision; some are specified by the covalent structure and others by Nuclear Magnetic Resonance (NMR) experiments (or X-ray crystallography which, however, requires crystallization). The output is a valid tertiary structure in a specified neighborhood of the input. Our approach should help in detecting outliers of the NMR experiments, and handles inputs with partial information. Moreover, our technique is able to bound the number of degrees of freedom of the conformation manifold. We have used numerical linear algebra algorithms for reasons of speed, and because they are well-implemented, fully documented and widely available. Our main tools include, besides distance matrices, structure-preserving matrix perturbations for minimizing singular values. Our MATLAB (or SCILAB) implementation is described and illustrated.AMS subject Classification: 92E10 Molecular structure, 92C40 Biochemistry, molecular biology, 65F15 Eigenvalues, eigenvectors, 15A18 Eigenvalues, singular values, and eigenvectors 相似文献
976.
Edith Gößnitzer Ales Krbavcic Winfried Wendelin Marija Krbavcic 《Monatshefte für Chemie / Chemical Monthly》2002,133(9):1177-1185
Summary. Novel N-(3-oxobutyl)-hydroxy- and acetoxypyrido[2,3-d]pyridazinones were synthesized and tested in vivo for their sedative and anticonvulsant activity. The Michael-type reaction of quinolinic acid hydrazide and methyl vinyl ketone afforded a mixture of two isomers, 5-hydroxy-N
7-(3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one and 8-hydroxy-N
6-(3-oxobutyl)-pyrido[2,3,-d]pyridazin-5-(6H)-one, in a ratio of 2:1 which were separated by crystallization. Subsequent acetylation of both isomers yielded the corresponding
5- and 8-acetoxy compounds. The structures of the compounds were proven and completely assigned on the basis of 1H, 13C, 15N NMR, and 1D NOE difference spectra as well as 2D C,H-correlation experiments. Preliminary pharmacological tests showed low
acute toxicity with a LD
50 > 1000 mg/kg in the mouse and sedative activity for the title compounds. 5-Acetoxy-N
7- (3-oxobutyl)-pyrido[2,3-d]pyridazin-8(7H)-one displayed a borderline anticonvulsant activity in the metrazole test model.
Corresponding author. E-mail: edith.goessnitzer@uni-graz.at
Received March 20, 2002; accepted April 3, 2002 相似文献
977.
采用乙酸乙酯为环型和线型聚苯乙烯的非良溶剂, 确定了Mark-Houwink方程分别为[η]_r=1.91×10~(-2)·M~(0.607)和[η]_l=4.06×10~(-2)·M~(0.572)。研究了环型和线型聚苯乙烯的激基缔合物的荧光效应。通过稀溶液中环型和线型高分子线团在柔顺性上存在着差异, 解释了二者之间在荧光效应方面的差异, 并根据实验结果,确定了(I_E/I_M)c→0~M关系式分别为(I_E/I_M)r,c→0=1.91+3.40×10~(-6)M和(I_E/I_M)l,c→0=2.15+3.05×10~(-6)M。 相似文献
978.
The differential equations and the boundary conditions for the nonequilibrium binary distribution function of an unsymmetrical binary electrolyte are derived from the Ebeling-Falkenhagen continuity equation. The connection between the Onsager reciprocal relation and the binary distribution functions is shown. Further, Feistel's result for thec logc contribution to the conductance is extended to unsymmetrical binary electrolytes. The reason for the difference between Feistel's and Chen'sc logc term is explained, and the significance of Onsager's reciprocal relation for the calculation ofc logc and higher-concentration contributions of the conductance is discussed. 相似文献
979.
Helmut Spreitzer Edith Rodinger Andrea Pichler Gerhard Buchbauer 《Monatshefte für Chemie / Chemical Monthly》1990,121(11):955-961
Summary The bicyclo[2.2.1]- and [2.2.2]-systems are part of numerous biological active substances. Continuing our syntheses in the isocamphane series the homologous isocamphanes of mecamylamine (1 a) and of the fungicidal bicyclic compound2 were synthesized. Furthermore the syntheses ofE-homoisosantalene (15) andE,E-homoisosantalol (16) are described. 相似文献
980.
A method has been developed for highly sensitive determination of haloperidol in human serum involving a simple extraction procedure followed by gas chromatographic separation. Target components were separated from the extracting solvents with a Van den Berg type solventless sample injector before introduction Into a DB-1 capillary separation column. A surface ionization detector (SID), which has highly selective sensitivity for Substituted amines, was employed for quantitation using bromperidol as an internal standard. Chloroform proved to be the best extracting solvent, yielding a quantitative detection limit of 5 ng/ml (S/N = 2). Comparison of the response to target compounds obtained by the SID, FTD (flame thermionic detector), and FID (flame ionization detector) showed the SID to be superior. 相似文献